JPS62235949A - Silver halide color photographic sensitive material which can be quickly processed and has excellent shelf life and the like - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material which can be quickly processed, has a good shelf life and is improved in processing stability by incorporating a silver halide of a prescribed grain size or compsn. into blue-, green- and red-sensitive silver halide emulsion layers and incorporating a specific compd. into at least one layer thereof. CONSTITUTION:The average grain size of the blue-sensitive silver halide emulsion layer in the photographic constituting layers on a substrate is specified to 0.20-0.65mum and the silver bromide content of the silver halide of the green- and red-sensitive silver halide emulsion layers is specified to 5-65mol%. The compd. expressed by the general formula I or II is incorporated into at least one layer of the photographic constituting layers. In the formulas, R<1>, R<2> are a hydrogen atom, alkyl group, R<3> is a halogen atom, aryl group, (n) is 0-5 integer, X, Y are the groups which can be released by hydrolysis. The silver chlorobromide or silver chloroiodobromide contg. 5-65mol% silver bromide or the mixture composed thereof is used for the silver halide contained in the green- and red-sensitive silver halide emulsion layers.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and in particular to a 3-pyrazolidone compound precursor (precursor).
This invention relates to a silver halide color photographic material containing.

Specifically, the present invention relates to a silver halogen color photographic light-sensitive material that can be rapidly processed, has good processing stability, has good storage stability, and provides high sensitivity.

[Prior art]

In recent years, there has been a desire in the industry for silver halide color photographic materials that can be processed quickly, have high image quality, have good storage stability, have excellent processing stability, and are low cost. In particular, silver halide color photographic materials that can be rapidly processed are desired.

In other words, silver halide color photographic light-sensitive materials are subjected to running processing in automatic processing machines installed in each laboratory, but as part of an effort to improve service to users, processing is carried out on the same day that processing is received. ``It is required that silver halide color photographic materials be processed and returned to the user, and in recent years, it has even been requested that the materials be returned within a few hours of receipt, and the development of silver halide color photographic materials that can be processed more and more rapidly is required. It's urgent. Furthermore, in running processing, there is a problem in that photographic properties vary greatly between laboratories or even within the same laboratory due to changes in the composition of the processing solution and fluctuations in conditions, making it impossible to obtain stable photographic performance. These changes in the composition of the processing solution and fluctuations in conditions are
This is thought to be due to elution and accumulation of photographic active substances from the light-sensitive material during development processing (running), or other causes. Therefore, it is required that the development time, temperature and pH of the developer, as well as the halogen concentration, especially the bromine ion concentration, etc. in the developer are highly controlled in order to accommodate variations in processing conditions. However, compared to the development time or the temperature and pH of the developer, the bromine ion concentration in the developer is difficult to quantify and difficult to measure, making it difficult to control. Therefore, it is particularly necessary to develop a silver halide color photographic light-sensitive material whose photographic performance has little dependence on bromine concentration and is highly process-stabilized.

Processing stability is a problem even with current processing times, but processing stability becomes more of a problem in rapid processing.

Furthermore, it is a matter of course that such processing-stabilized silver halide color photographic materials are required to be economically provided at low cost.

Therefore, if we look at the conventional technology for silver halide color photographic materials that can be processed quickly, for example,
Silver halide micrograining technology as described in No. 1-77223, ■ JP-A-58-184142, JP-A-56-1
1-Aryl-3-pyrazolidones having a specific structure as described in JP-A-56-64339 in silver halide color photographic light-sensitive materials. Addition technology, and JP-A-57
-144547, 58-50534, 58-5
0535 and No. 58-50536 are known, in which 1-arylpyrazolidones are added to silver halide color photographic materials; A technique of using a color development accelerator when developing a material using an aromatic primary amine color developing agent is also known. For example, such color development accelerators are described in U.S. Pat.
, No. 970, No. 2,515゜147, No. 2,496.
No. 903, No. 4,038.075, No. 4゜119.4
No. 62, British Patent No. 1,430.998, British Patent No. 1,455
．． No. 413, JP-A-53-15831, JP-A No. 55-62
No. 450, No. 55-62451, No. 55-62452
No. 55-62453, No. 51-12422, No. 55-62453, Special Publication No. 51-12422, No. 5
There are compounds described in No. 5-49728 and the like.

However, when using the conventional techniques (1) or (2), although the processing time is shortened, the processing stability is poor, and there are also problems with fogging and storage stability in same-day performance.

When the low silver bromide emulsion of the previous period (2) is used, the amount of bromide ions eluted into the processing solution from the silver halide color photographic light-sensitive material containing the low silver bromide emulsion is small (the concentration of bromide ions in the processing solution is Although rapid processing can be achieved because the bromide concentration can be set low, processing stability is poor if a silver halide color photographic light-sensitive material containing a low silver bromide emulsion is processed using a processing solution with a low bromide ion concentration. .

Processing stability here refers to the degree of variation in sensitometry with respect to variations in processing solution composition, PLL, temperature, bromide ion concentration, etc., and to contamination of other compounds other than the processing solution composition.

Further, when fine-grained silver halide of the previous period (2) was used, there was a drawback that processing stability was poor, and the sensitivity deteriorated as the grains became finer.

Among these conventional techniques, one that has a particularly large development accelerating effect is the method of incorporating 3-pyrazolidones into photographic light-sensitive materials. The oxidation products may act on silver halide to generate fog nuclei, which may themselves become oxidized and lose their effectiveness, or the oxidation products may bleach and desensitize the photosensitive nuclei of silver halide. , sufficient photographic performance could not be obtained.

In order to solve this problem, a method has been proposed in which, instead of using 3-pyrazolidones themselves, they are incorporated as a precursor that releases 3-pyrazolidones when decomposed by an alkali. The characteristics of these compounds are that they do not act on silver 10genide before the development process and do not undergo air oxidation, and by optimizing the compounds, the timing of release during development can be controlled. can give. Examples of these precursors include:
The following are known: That is, JP-A-55-53
330, 55-73048, 57-135949
, 57-179842, 58-1139, 58
-1140, 58-117544, 57-197
32, 57-40245, 59-93442, 5
9-104641, 59-116649, 59-
121328, 59-137945, 59-14
0445, 59-197037, 59-198
453, 59-201057, 59-20245
9, 59-218439, 59-219741
, 60-41034, 60-53950, 6
0-53951, 61-32839, CB-2073
734, EP 45129, BE-863052, US
Compounds described in P 4,358,525, RD (Research Disclosure)-181042, etc. are known.

However, using only these compounds does not provide all the characteristics such as rapid development and sufficient photographic performance, that is, high sensitivity, low fog, good processing stability, and good storage stability. It was impossible to obtain a satisfactory color photographic material.

[Problem that the invention seeks to solve]

The present invention has been made in view of the above, and a technical problem is to provide a silver halide color photographic material that can be rapidly processed, has good storage stability, and has improved processing stability. do.

[Means for solving problems]

The above technical object is achieved by the following silver halide color photographic light-sensitive material of the present invention.

That is, the silver halide color photographic light-sensitive material of the present invention has photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support. In the silver halide color light-sensitive material, the average grain size of silver halide in the blue-sensitive silver halide emulsion layer is 0.20 to 0.65 μm, and the average grain size of silver halide in the blue-sensitive silver halide emulsion layer is 0.20 to 0.65 μm, and The silver bromide content of silver halide in the silver emulsion layer is 5 to 65 mol%, and at least one of the photographic constituent layers contains the following formula -i (
This is a silver halide color photographic light-sensitive material characterized by containing a compound represented by 1) or (If).

[In the formula, R1 and R2 each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group, R3 represents a halogen atom, an alkyl group, or an aryl group, R4 represents a hydrogen atom or an aryl group, and n is 0 to Represents an integer of 5, X
and Y represents a group that can be separated by hydrolysis. ] The silver halide color photographic light-sensitive material of the present invention uses a 3-pyrazolidone precursor represented by the general formula (I) or (n) as described above, and also contains a specific particle size as described above in each color-sensitive layer. By using silver halide grains of It is.

It was unexpected and surprising that a photosensitive material satisfying all of the above-mentioned problems could be obtained by the present invention.

The present invention will be explained in more detail below.

The silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention has an average grain size (average grain size) of 0.20-0.
65 it m, preferably 0.30-0.50 p
It is m. When the average particle size exceeds 0.65 .mu.-, the processing stability is poor, and particularly when the amount of potassium bromide varies, the processing stability is significantly deteriorated. On the other hand, the average particle size is 0.20μ
If it is less than m, the sensitivity of the blue-sensitive silver halide emulsion layer will be insufficient, resulting in magenta color turbidity.

The average grain size of the silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention can be measured by various methods commonly used in the technical field for the above purpose. A representative method is Loveland's "Particle Size Analysis Method" 8, S. T. M., Symposium on Light Microscopy, 1955, 94-1.
22 pages or "Theory of the Photographic Process" by Mies and James, 3rd edition, published by Macmillan (1966)
Some of them are listed in Chapter 2 of . The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The silver halide used in the present invention may be a polydisperse emulsion in which the average grain size is distributed over a wide range, but a monodisperse emulsion is preferred.

In the present invention, the above-mentioned monodisperse silver halide grains are those in which most of the silver halide grains appear to have the same shape when the emulsion is observed using an electron microscope, have uniform grain sizes, and have the following formula: It has a particle size distribution as defined. That is, if the standard deviation S of the grain size distribution is divided by the average grain size 7, then □ ≦ 0.15 The grain size here has the same meaning as the grain size described above regarding the average grain size, and the cubic silver halide In the case of a particle, the length of its side, or in the case of a particle with a shape other than a cube, the length of one side when converted to a cube having the same volume, and the individual particle size in this sense When is ri and the number is ni, 7 is defined by the following formula.

Σni ri Σni The relationship between particle size distribution is described in "Empirical relationship between sensitometric distribution and particle size distribution in photography" The Photographic Journal, Volume LXXIX (1949) 330-3
In the method described in the paper by Tribel and Smith on page 38,
You can decide this.

The silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention has a silver bromide content of 5 to 65 mol%, for example, silver chlorobromide. , silver chloroiodobromide or a mixture thereof can be used.

In the present invention, one or both of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer may be composed of two or more layers. In the present invention, the silver bromide content refers to the total silver bromide in each layer in the total amount of halide contained in each of the total green light-sensitive silver halide emulsion layer and the total red light-sensitive silver halide emulsion layer. It refers to the content rate of When the silver bromide content exceeds 65 mol %, processing stability deteriorates, magenta color becomes cloudy, and image quality deteriorates. On the other hand, when the silver bromide content is less than 5 mol %, processing stability deteriorates significantly.

When the silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention is silver chloroiodobromide, the silver iodide content exceeds 2 mol%. It is preferable that the amount is zero, and more preferably 1 mol % or less.

The silver bromide content of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is preferably 20 to 60 mol%, more preferably 30 to 55 mol%.

The silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention is also monodisperse like the silver halide contained in the blue-sensitive silver halide emulsion layer. Preferably.

The composition of the silver halide contained in the blue-sensitive silver halide emulsion layer is not particularly limited, and any composition can be used. For example, silver bromide, silver chlorobromide, or silver chloroiobromide can be used. or a mixture thereof, silver chlorobromide is preferred, particularly silver bromide content of 30 to 95 mol%
belongs to. Furthermore, the blue-sensitive silver halide emulsion layer in the present invention may consist of two or more layers.

The average grain size of the silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is not particularly limited, but is preferably 0.1 to 2 μm, more preferably 0.2 to 1 μm. Particularly preferably 0.25 to 0.8 μm
It is.

The compound represented by the general formula (1) or (II) used in the silver halide color photographic light-sensitive material of the present invention is a precursor of a 3-pyrazolidone compound.

The compounds represented by the general formula CI) or (II) of the present invention will be described in detail below.

The compound represented by the general formula (1) or (II) of the present invention can be used, for example, in JP-A-55-53330 and JP-A-55-73048.
, 57-135949, 57-179842,
58-1139, 58-1140, 58-11
7544, 57-19732, 57-40245
, 59-93442, 59-10461, 59-
116649, 59-121328, 59-1
37945, 59-140445, 59-19
7037, 59-198453, 59-2010
57, 59-202459, 59-218439
, 59-219741, 60-41034, 60-53950, 60-53951, 61-32
839, CB-2073734, EP 45129,
BE-863052, USP 4.358,525, R
D (Research Disclosure) -181042, etc.

Specific examples of the compound represented by the general formula (I) or (II) are shown below, but the present invention is limited thereto. ) is 0.3 to Ig/n? in the entire photosensitive silver halide emulsion layer. It is preferable that That is, in order to obtain excellent image quality, the amount of silver must be Ig/r.
The amount of silver is preferably 0.3 g/nf or more in order to obtain a high maximum density and high sensitivity. In the present invention, the silver amount is particularly preferably 0.4 to 0.8 g/I.

Silver halide compositions preferably used in the present invention include silver chlorobromide and silver chloroiodobromide. Furthermore, a combination mixture may be used in which separately formed silver chloride and silver bromide are mixed. That is, when the silver halide emulsion according to the present invention is used in color photographic paper, particularly fast developability is required, so it is preferable that the halogen composition of the silver halide contains chlorine atoms, and at least one
Particular preference is given to silver chlorobromide or silver chloroiodobromide containing % silver chloride.

The monodisperse silver halide grains preferably used in the present invention may be obtained by any conventionally known preparation method such as an acidic method, a neutral method, or an ammonia method.

Alternatively, for example, seed particles may be produced using an acidic method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and the amount of silver ions commensurate with the growth rate of silver halide grains is controlled, for example, as described in JP-A-54-48521. It is preferable to implant and mix the and halide ions sequentially and simultaneously.

The silver halide grains according to the present invention are prepared, for example, as described above. A composition containing silver halide grains as described above is hereinafter referred to as a silver halide emulsion.

These silver halide emulsions contain activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, Polyamines, etc.; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothiol-3-
Aggravating agents such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chloroparadate, potassium chlorooleate and sodium chloroparadate (consisting of these Depending on the amount, these substances act as aggravating agents or fog suppressants. It may also be chemically aggravated by using a combination of drugs, etc.).

The silver halide emulsion used in the present invention is chemically ripened by adding a sulfur-containing compound, and contains a small amount (both of which have one type of hydroxytetrazaindene and a mercapto group) before, during, or after the chemical ripening. It may contain at least one nitrogen heterocyclic compound.

In order to impart photosensitivity to the desired wavelength range of the silver halide used in the present invention, a suitable aggravating dye is added to each mole of silver halide at 5X10-'' to 3X10-'
Optical sensitization may be achieved by adding molar amounts. Various sensitizing dyes can be used, and each sensitizing dye is
It can be used in one species or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following.

That is, examples of exacerbating dyes used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929.080, US Pat. No. 2,231,658, US Pat. , No. 2,519.001, No. 2
, No. 912.329, No. 3.656.959, No. 3,
No. 672.897, No. 3,694.217, No. 4.0
No. 25,349, No. 4,046,572, British Patent 1
, No. 242.588, Special Publication No. 44-14030, No. 5
2-24844 etc. can be mentioned. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include U.S. Pat.
Typical examples thereof include cyanine dyes, merocyanine dyes and composite cyanine dyes as described in British Patent No. 505.979 and British Patent No. 505.979. Furthermore, as an enhancing dye used in a red-sensitive silver halide emulsion, for example, US Pat. No. 2.269.
No. 234, No. 2,270.378, No. 2,442,7
No. 10, No. 2,454.629, No. 2.776.28
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 0. Furthermore, U.S. Pat. No. 2,213.
No. 985, No. 2,493.748, No. 2,519.0
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 01, West German Patent No. 929.080, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination. Combinations of enhancing dyes are often used, especially for supersensitization purposes.

Typical examples are U.S. Pat. No. 2.688.545 and U.S. Pat.
No. 77.229, No. 3,397.060, No. 3,52
No. 2,052, No. 3,527.641, No. 3.617
, No. 293, No. 3,628.964, No. 3.666.
No. 480, No. 3,672,898, No. 3,679,4
No. 28, No. 3,703,377, No. 3,769,30
No. 1, No. 3,814,609, No. 3.837.862
No. 4,026,707, British Patent No. 1.344.2
No. 81, No. 1, No. 507, No. 803, Special Publication No. 43-4
No. 936, No. 53-12375, JP-A-52-110
No. 618 and No. 52-109925.

The silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent Nos. 584, 609 and 1,27.
7.429, JP-A-48-85130, JP-A No. 49-9
No. 9620, No. 49-114420, No. 49-129
No. 537, No. 52-108115, No. 59-2584
No. 5, U.S. Patent No. 2,274,782, U.S. Patent No. 2,533.
No. 472, No. 2,956.879, No. 3,125.4
No. 48, No. 3,148,187, No. 3,177.07
No. 8, No. 3,247.127, No. 3,540°887
No. 3,575.704, No. 3,653,905, No. 3゜718.472, No. 4.071,312,
4,070.352.

Each of the silver halide emulsion layers in the present invention can contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

In the present invention, conventionally known yellow couplers, magenta couplers, and cyan couplers can be used as the couplers.

These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and in combination with these couplers, it is also possible to use diffusible dye-releasing type couplers.

The yellow couplers include conventionally used closed ketomethylene compounds, active point -〇-aryl substituted couplers called so-called 2-equivalent type couplers, active point -〇-acyl substituted couplers, active point hydantoin compound substituted couplers, Active point urazole compound substituted couplers, active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -0-sulfonyl substituted couplers, etc. can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat.
875.057, 3,265.506, 3,4
No. 08.194, No. 3,551.155, No. 3,58
No. 2.322, No. 3,725.072, No. 3,891
, 445, West German Patent No. 1.547,868, West German Application No. 2,219.917, West German Patent Application No. 2,261.361,
No. 2,414,006, British Patent No. 1,425,020
No., Special Publication No. 1978-10783, Japanese Patent Publication No. 47-2613
No. 3, No. 48-73147, No. 51-102636, No. 50-6341, No. 50-123342, No. 5
No. 0-130442, No. 51-21827, No. 50-
No. 87650, No. 52-82424, No. 52-115
Examples include those described in No. 219 and No. 58-95346.

Examples of magenta couplers used in the present invention include pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indacylon compounds.

These magenta couplers are similar to the yellow couplers 4
Not only an equivalent type coupler but also a 2-equivalent type coupler may be used. A specific example of a magenta coupler is US Patent 2.
, No. 600.788, No. 2,983.608, No. 3,
No. 062.653, No. 3,127.269, No. 3.3
1L No. 476, 3,419.391, 3,519
．． No. 429, No. 3558.319, No. 3,582.
No. 322, No. 3,615.506, No. 3,834,9
No. 08, No. 3,891.445, West German Patent No. 1,810
．． No. 464, West German patent ratio # (OL S) 2,408
, No. 665, No. 2.417.945, No. 2,418.
No. 959, No. 2,424.467, Special Publication No. 1977-1960
No. 31, JP-A-51-20826, JP-A No. 52-5892
No. 2, No. 49-129538, No. 49-74027, No. 50-159336, No. 52-42121, No. 49-74028, No. 50-60233, No. 51-
No. 26541, No. 53-55122, Patent Application No. 55-1
Examples include those described in No. 10943 and the like.

Further, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers include U.S. Patent Nos. 2,369.929 and 2.
, 434.272, 2.474.293, 2.
521.908, 2,895.826, 3.0
No. 34,892, No. 3,311.476, No. 3.45
No. 8.315, No. 3,476.563, No. 3,583
．． No. 971, No. 3,591゜383, No. 3,767.
411, 4,004, 929, West German Patent Application (OLS) 2,414.830, 2,454
．． No. 329, JP-A-48-59838, JP-A No. 51-26
No. 034, No. 48-5055, No. 51-146827
No. 52-69624, No. 52-90932, No. 5B-95346, and the like.

In order to incorporate these couplers into the silver halide emulsion in the present invention, if the couplers are alkali-soluble, they may be added as an alkaline solution (or if they are oil-soluble, they may be added as an alkaline solution, for example in the US). Patent No. 2.322.0
No. 27, No. 2.801.170, No. 2.801.
No. 171, No. 2.272.191 and No. 2.3
It is preferable to dissolve the coupler in a high-boiling point solvent, optionally in combination with a low-boiling point solvent, according to the method described in each specification of No. 04.940, disperse it in the form of fine particles, and add it to the silver halide emulsion. At this time, other hydroquinone derivatives, ultraviolet absorbers, anti-browning agents, etc. may be used in combination as necessary. It is also possible to use a mixture of two or more couplers. Further, to explain in detail the preferred method of adding couplers in the present invention, one or more of the couplers are added to an organic acid amide along with other couplers, hydroquinone derivatives, brown preventive agents, ultraviolet absorbers, etc. as necessary. , carbamates, esters, ketones,
Urea derivatives, ethers, hydrocarbons, etc., especially di-n-
Butyl phthalate, triresyl phosphate, triphenyl phosphate, di-isooctyl azelate,
Di-n-butyl sebacate, tri-n-hexyl phosphate, N,N-di-ethyl-caprylamidobutyl, N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3- High boiling point solvents such as pentadecyl phenylethyl ether, 2.5-di-5ee-amylphenylbutyl ether, monophenyl-di-0-chlorophenyl phosphate or fluoroparaffin, and/or
Or low boiling point materials such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, etc. Anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate, and/or hydrophilic binders such as gelatin, dissolved in a solvent. The silver halide emulsion is mixed with an aqueous solution containing the compound, emulsified and dispersed using a high-speed rotating mixer, colloid mill, ultrasonic dispersion device, etc., and then added to a silver halide emulsion.

In addition, the above couplers may be dispersed using a latex dispersion method. The latex dispersion method and its effects are described in JP-A-49-74538, JP-A-51-59943, and JP-A-54.
-32552 Specification Publication and Research Disclosure, August 1976, 14850. Pages 77-79.

Suitable latexes include, for example, styrene, acrylate,
n-butyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-(2-(2-methyl-4 -oxopentyl)]acrylamide, 2-acrylamide-2-
Homopolymers, copolymers and terpolymers of monomers such as methylpropanesulfonic acid and the like.

The silver halide color photographic material of the present invention may contain various other photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent whitening agents, color image browning inhibitors, antistatic agents, etc., as described in Research Day, Sproger Magazine No. 17643,
Hardeners, surfactants, plasticizers, wetting agents, etc. can be used.

In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Examples include cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.

Examples of the support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, such as a glass plate, and cellulose acetate. , polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc., and these supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also, U.S. Patent No. 2.761.791;
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 941.898.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photosensitive material for photographic paper, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-light-sensitive silver halide emulsion layer are arranged sequentially from the support side. is preferred.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers.

Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included.

There are no particular limitations on the processing method for the silver halide color photographic light-sensitive material according to the present invention, and any processing method can be applied. For example, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and/or stabilization treatment if necessary; bleaching and fixing are performed separately after color development; A method of performing water washing and/or stabilizing treatment; or a method of performing prehardening, neutralization, color development, stop fixing, water washing, bleaching, fixing, water washing, post hardening, water washing, color development, water washing, supplementary color development Developing, stopping,
Either method can be used, such as a method in which bleaching, fixing, washing, and stabilization are carried out in this order, or a method in which the developed silver produced by color development is subjected to halogenation bleaching, and then color development is performed again to sensitize the amount of produced dye. It may also be processed.

The color developing solution used for processing the silver halide emulsion of the present invention is an alkaline aqueous solution containing a color developing agent and preferably having a pH of 8 or more, more preferably a pH of 9 to 12.

The aromatic primary amine developing agent used as the color developing agent is a compound having a primary amine group on an aromatic ring and has the ability to develop exposed silver halide. All compounds forming such compounds may be added.

The color developing agent mentioned above is typically p-phenyl diamine type, and the following are preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-methanesulfonamidoethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-
N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N.

N-dimethylaniline, N-ethyl-N-β-[β-(
β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and salts thereof such as sulfates, hydrochloride, sulfite,
p-) luenesulfonate and the like.

Furthermore, for example, JP-A-48-64932, JP-A-50-1
31526, No. 51-95849, and those described by Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951) are also mentioned as representative examples.

The amount of these aromatic primary amino compounds to be used depends on where the activity of the developer is set; however, in order to increase the activity, it is preferable to increase the amount used. The amount used ranges from 0.0002 mol/l to 0.7 mol/β. Moreover, two or more compounds can be used in appropriate combination depending on the purpose. For example, 3-methyl-4-amino-N,N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-nee! -Lou N-β
-Hydroxyethylaniline, etc. can be freely used in combination depending on the purpose.

The color developing solution used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites,
Alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol,
A water softener, a thickening agent, a development accelerator, etc. can also be optionally included.

However, it is preferable that benzyl alcohol is not added to the color developing solution.

In other words, benzyl alcohol has a pollution load value of BO
D and COD are high, and benzyl alcohol has low water affinity, so diethylene glycol and triethylene glycol are required as solvents, but glycols also have high BOD and COD, so they are discarded due to overflow. The processing liquid used in this process has the problem of environmental pollution. Furthermore, benzyl alcohol has low solubility in a developer and requires a long time to prepare a developer or a replenisher, which poses operational problems. Furthermore, if the amount of replenishment is large, the number of times replenishment liquid must be prepared increases, which also becomes a burden on the work.

Therefore, environmental pollution and operational problems are eliminated by substantially not containing benzyl alcohol in the color developer, which is very preferable.

Examples of additives other than those mentioned above that are added to the color developer include bromides such as potassium bromide and azomonium bromide;
Compounds for quick processing solutions such as alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-penzotriazole, ■-phenyl-5-mercabutotetrazole, as well as anti-staining agents, anti-sludge agents, and preservatives. , baking soda effect accelerator, chelating agent, etc.

Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. ing. Representative examples of the above aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl ether diaminetetraacetic acidethylenediaminetetrapropionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acid pentasodium saltnitrilotriacetic acid sodium saltBleaching solution contains various additives along with the above bleaching agents. It may also contain an agent. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. As in the case of the above-mentioned bleaching solution, various other additives such as pHFl buffer, type l agent, brightener, antifoaming agent, surfactant, preservative, chelating agent, stabilizer, organic solvent, etc. Add,
It may be included.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned.

Color development of the silver halide color photographic light-sensitive material of the present invention,
The processing temperature of bleach-fixing (or bleaching, fixing), and various processing steps such as washing with water, stabilization, and drying, which are carried out as necessary, is preferably carried out at 30° C. or higher from the viewpoint of rapid processing.

The silver halide color photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58
-14834, 58-105145, 58-1
No. 34634 and No. 58-18631 and patent application 1973
A stabilizing treatment as an alternative to washing may be performed as shown in Japanese Patent No. 8-2709 and Japanese Patent No. 59-89288.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Example 1 On a paper support laminated on both sides with polyethylene, the following layers were sequentially applied from the support side to prepare a silver halide color photographic light-sensitive material sample N11l.

Layer 1...1.2g/rI? gelatin, 0.32g/
blue-sensitive silver chlorobromide emulsion (in terms of silver, the same applies hereinafter)
0.80 g/n? dissolved in dioctyl phthalate with particle size 0°8 mm) and 0.50 g/n? yellow coupler (
A layer containing Y-1).

Layer 2 - 0.70g/rrr gelatin, 8mg/
rrr irradiation dye, (AI-1) and 4m
g/n? An intermediate layer consisting of (AI-2).

Layer 3...1.25g/m gelatin, 0.20g/-
green-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%), 0
．． 0,6 dissolved in 30g/g dioctyl phthalate
2g1rd layer containing magenta coupler (M-1).

Layer 4: Intermediate layer consisting of 1.20 g/m of gelatin.

Layer 5...1.20g/rd gelatin, 0.30g/
CD red-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%)
, 0.20 g/n (of dioctyl phthalate).

Layer 6...1.00g 7m of gelatin and 0.20g/
0.30g/dissolved in rd dioctyl phthalate
A layer containing an ultraviolet absorber (UV-1) of rrl.

(AI-2) (UV-1) As a hardening agent, 2.4-dichloro-6-hydroxy-5-) riazine sodium was added in layers 2.4 and 7.
Each was added in an amount of 0.017 g per 1 g of gelatin.

In addition, the grain size of silver halide in layer 1 and the silver bromide content of silver halide in layers 3 and 5 in sample level 1 were changed as shown in Table 1, and in layer 2, 8 mg/rrr of the present invention Samples 11m2 to 8 were prepared in the same manner as sample N11l above, except that the compounds shown in Table 1 were added.

Each of the photosensitive material samples N11l to N8 was exposed through an optical wedge and then processed in the following steps.

Processing process (35℃) Color development 1 minute and 1 minute 30 seconds bleach fixing
Washing with water for 1 minute Drying for 1 minute at 60 to 80°C for 2 minutes The composition of each treatment solution is as follows.

[Color developer A]

Pure water 800m A hydroxyamine sulfate 2.0g Potassium bromide
1.5g Sodium chloride 1.0g Potassium sulfite 2.0g Triethanolamine 2.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 1-hydroxyethylindene-1,1 '-diphosphonic acid (60% aqueous solution) 1.5n1 potassium carbonate
32g Whitex BB (50% aqueous solution) 2ml (fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to make 11 and 20% potassium hydroxide or 10
% dilute sulfuric acid to adjust po=11.2.

[Bleach-fix solution]

Pure water 550m A ethylenediaminetetraacetic acid iron(III) Ammonium 65g Ammonium thiosulfate 85g Sodium hydrogen sulfite 10g Sodium metabisulfite 2g Ethylenediaminetetraacetic acid-disodium 0g Sodium bromide 10g Add pure water to make 11, and add to ammonia water or dilute sulfuric acid. Tep
Adjust to H=7.0.

Sensitometry was performed on each sample after the above treatment,
The sensitivity of the blue-sensitive emulsion layer was determined.

In addition, for the above samples No. 1 to No. 8, 50°C, 70% R
Forced deterioration by leaving it under the conditions of 1 for 6 days,
The storage stability of each raw sample was evaluated by performing the same treatment as above (however, the color development time was only 1 minute and 30 seconds).

The results are shown in Table 1.

Phenidone, a comparative compound, has the following structure.

As is clear from Table 1, when using a silver halide emulsion other than the present invention, that is, one in which the grain size and halogen composition of each color-sensitive layer are outside the scope of the present invention, even if phenidone is contained (sample 2) Even if any of the phenidone precursors of the present invention is used (sample 11h3), the photographic performance (sensitivity) is insufficient when rapid development is performed for 1 minute. On the other hand, when using the silver halide emulsion of the present invention and the phenidone precursor of the present invention, the details according to the present invention,
In other words, it can be seen that Samples 1'&h6-8 can obtain sufficient sensitivity even after 1 minute of development and are excellent in rapid processability.

Although sample number 5 to which phenidone was added has a certain degree of rapid processing properties, the sensitivity decreases significantly on the same day, and the sensitivity decreases significantly during storage. As can be understood by combining the data with sample number 2, the sensitivity of the sample to which phenidone was added is low on the same day, and the sensitivity decreases significantly during storage.

On the other hand, it can be seen that Samples 11h6 to 11h8 according to the present invention to which the phenidone precursor of the present invention was added had very little decrease in sensitivity on the same day and also had good storage stability.

Even if the emulsion of the present invention was used, the emulsion without the phenidone precursor of the present invention (Sample No. 4) had insufficient rapid processability.

Example 2 After exposing 8 fish from the sample Nal of the present invention to light through an optical wedge, they were treated in the next step using color developer B in which 40 mg/l of phenidone was added to the color developer A.

Processing process (35℃) Color development 45 seconds and bleach fixing for 1 minute 15 seconds
Washing with water for 1 minute Drying for 1 minute at 60-80° C. for 2 minutes Sensitometry was performed on each sample after the above treatment to determine the sensitivity (S) and maximum density (Dm) of the blue-sensitive emulsion layer. The results are shown in Table 2.

Table 2 *7 Sensitivity (S) is based on the sensitivity of sample size 1 developed for 1 minute and 15 seconds as 100.

From Table 2, it can be seen that the same tendency as in the previous example is observed in this example, and the sample of the present invention exhibits excellent photographic performance.

Furthermore, as is clear from Table 2, samples Nos. 2 and 1lh5 containing phenidone do not have the highest density after development.

On the other hand, the sample of the present invention can finally obtain a sufficient maximum concentration.

Example 3 Regarding sample floors 1 to 8, the concentration of potassium bromide in the color developer B was set to 0.6, 1.3, and 2.6.
Processing was carried out in the same manner as above using a color developing solution with the only difference that the ratio was 1 g/1. (However, the development time is 45
(seconds only) Sensitometry was performed on each sample obtained using a conventional method. Table 3 shows gamma-9 values at each potassium bromide concentration.

Table 3 Sensitometric slope from 0.8 to 1.8. same as below.

Book 9 Fluctuation; Δγ = △r, + △γ2 △γ1 = 1 γ (1, 3) - γ (0, 6) 1 to γt = I r (1, 3) - γ (2, 6)
1 Here, for example, γ(1,3) is the odor 46 potassium B
It represents the gamma value when t is 1.3 g/l.

As is clear from Table 3, when the silver halide emulsion of the present invention is used, the gamma value fluctuates greatly in response to fluctuations in the potassium bromide concentration of the processing solution, and even when the compound of the present invention is used ( Even sample 11h3) cannot be said to be sufficient during the fluctuation.

In addition, sample No. 4 using the silver halide emulsion of the present invention shows a significant improvement in processing variation characteristics compared to sample No. From 6 to 11h8, the processing variation characteristics are greatly improved.

In addition, in samples No. 2 and No. 5, a decrease in gamma value was observed due to the addition of phenidone, but in samples No. 6 to N18 according to the present invention, which used the precursor of the present invention, sufficiently high gamma values were obtained. It will be done.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to obtain a silver halide photographic material that can be rapidly processed, has good storage stability, and has improved processing stability.

Procedure Neho (Method) June 19, 1986 Director General of the Patent Office Michibu Uga 1, Indication of the case 1986 Patent Application No. 78439 3, Relationship with the person making the amendment Patent applicant Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 5, Date of amendment order Voluntary action 6, Subject of amendment Specification procedure Principal author (spontaneous) October 6, 1985 1, Indication of the case 1988 Year Patent Application No. 078439 2 Title of the invention Silver halide color photographic light-sensitive material that can be processed rapidly and has excellent storage stability 3 Relationship with the person making the amendment case Patent applicant address 1-chome Nishi-Shinjuku, Shinjuku-ku, Tokyo 26 number 2 name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent (1) Specification (referring to the revised specification submitted on June 19, 1985), pages 18, 20, 22, and 2
Edit each of the three pages as shown in the attached sheet.

(2) Correct "Adjustment method" in the second line from the top of No. 32 to "Preparation method".

(3) Same, 8th line from the top of No. 58 "Aniline sulfate" of "Aniline sulfate 8.OgJ Correct to.

that's all

Claims (1)

[Scope of Claims] A silver halide color light-sensitive material having photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support. , the average grain size of the silver halide in the blue-sensitive silver halide emulsion layer is 0.20 to 0.65 μm, and the average grain size of the silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 0.20 to 0.65 μm. The silver bromide content is 5 to 65 mol%, and at least one of the nuclear photographic constituent layers contains the following general formula (
A silver halide color photographic material containing a compound represented by I) or (II). General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are each independently a hydrogen atom, unsubstituted or Represents a substituted alkyl group, R^3 represents a halogen atom, alkyl group, or aryl group, R^4 represents a hydrogen atom or an aryl group, n represents an integer from 0 to 5, and X and Y represent hydrolyzed Represents a group that can be separated by ]